Composition for forming anchor coat layer, and laminate having anchor coat layer

Abstract

To provide a laminate having an anchor coat layer containing a chlorinated polyolefin-based resin (for example, overlap film) which can improve printability in a part where ink is overcoated and scratch resistance in a part where ink is not overcoated, while securing adhesion as a laminated film, and a composition for forming an anchor coat layer for forming an anchor coat layer constituting the laminate.SOLUTION: A composition for forming an anchor coat layer forming an anchor coat layer arranged between a polyolefin film and an ink layer contains a binder resin and an organic solvent, wherein the binder resin contains a chlorinated polyolefin resin, and any one resin of a rosin-based resin and a ketone resin.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition for forming an anchor coat layer and a laminate having an anchor coat layer. [Background technology]

[0002] Overwrap film is a type of packaging material that is attached to various adherends, such as containers containing food or daily necessities, by heat shrinking. For example, many cup containers containing instant noodles are wrapped and packaged with an overlap film provided with a design print layer such as a picture, trademark, product description, etc. Incidentally, an overlap film using a polyolefin film such as a heat-shrinkable polyolefin film is known. When polyolefin films are corona-treated, problems can occur during post-processing, such as when the film is sealed with a fusing heater and packaged, as the corona treatment can cause the seal to peel off, resulting in poor packaging. Therefore, printing must be performed without corona treatment. However, without corona treatment, the adhesion between the polyolefin film and ink layers, such as design print layers, is poor. Therefore, measures must be taken to improve the adhesion between the polyolefin film and ink layers, such as design print layers. Therefore, a configuration in which an anchor coat layer is provided between the heat-shrinkable polyolefin film and the design print layer can be considered. For example, an overlap film has been proposed that has a heat-shrinkable polyolefin film, an anchor coat layer laminated adjacent to the heat-shrinkable polyolefin film, and a design print layer laminated adjacent to the anchor coat layer (see, for example, Patent Document 1). In Patent Document 1, the anchor coat layer contains a chlorinated polyolefin resin. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-141403 Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors have investigated an overlap film having an anchor coat layer containing a chlorinated polyolefin resin as disclosed in the above-mentioned Patent Document 1. As a result, although the anchor coat layer containing the chlorinated polyolefin resin has excellent adhesion to the polyolefin film, it cannot be said that the printability when ink is reapplied is fully satisfactory, and there is room for improvement. There is also room for improvement in the scratch resistance of the areas where ink is not reapplied. An object of the present invention is to provide a laminate (e.g., an overlap film) having an anchor coat layer containing a chlorinated polyolefin resin, which can improve the printability of areas where ink is reapplied and the scratch resistance of areas where ink is not reapplied, while ensuring the adhesion of the laminate film, and to provide a composition for forming an anchor coat layer for forming the anchor coat layer that constitutes the laminate. [Means for solving the problem]

[0005] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that by including a specific resin in addition to a chlorinated polyolefin resin as a binder resin constituting a composition for forming an anchor coat layer, a laminate (e.g., an overlap film) having an anchor coat layer formed from a composition for forming an anchor coat layer containing the binder resin can solve the above-mentioned problems of the present invention, and have thus completed the present invention.

[0006] That is, the present invention includes the following aspects. [1] A composition for forming an anchor coat layer to be disposed between a polyolefin film and an ink layer, Contains a binder resin and an organic solvent, The composition for forming an anchor coat layer contains a binder resin selected from the group consisting of a chlorinated polyolefin resin, a rosin resin, and a ketone resin. [2] The composition for forming an anchor coat layer according to [1], wherein the binder resin further contains at least one resin selected from the group consisting of a cellulose resin, a polyurethane resin, a polyamide resin, an acrylic resin, a polyester resin, and a cyclized rubber. [3] The composition for forming an anchor coat layer according to [1] or [2], wherein the organic solvent contains at least one of an aliphatic hydrocarbon solvent, an ester solvent, an alcohol solvent, and a glycol ether solvent. [4] The composition for forming an anchor coat layer according to any one of [1] to [3], further comprising at least one of wax and silica. [5] A laminate comprising a polyolefin film, an anchor coat layer, and an ink layer laminated in this order, The anchor coat layer is a layer formed using the composition for forming an anchor coat layer according to any one of [1] to [4]. [6] The laminate according to [5], wherein the polyolefin film is a heat-shrinkable film. [7] The laminate according to [5] or [6], wherein the ink layer contains at least one of a ketone resin, a cellulose-based resin, and a polyamide resin. [Effects of the Invention]

[0007] The present invention can provide a laminate (e.g., an overlap film) having an anchor coat layer containing a chlorinated polyolefin resin, which can improve the printability of areas where ink is reapplied and the scratch resistance of areas where ink is not reapplied, while ensuring the adhesion of the laminate film, and a composition for forming an anchor coat layer for forming the anchor coat layer that constitutes the laminate. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present invention will be described in detail below. Note that the following explanation of the constituent elements is an example for explaining the present invention, and the present invention is not limited to these contents.

[0009] (Anchor Coat Layer Forming Composition) The anchor coat layer-forming composition of the present invention is a composition used to form an anchor coat layer disposed between a polyolefin film and an ink layer. A detailed description of a "laminate" (eg, an overlap film) having a polyolefin film, an ink layer, and an anchor coat layer disposed therebetween will be provided below. The anchor coat layer-forming composition of the present invention contains a binder resin and an organic solvent. The binder resin contains a chlorinated polyolefin resin and at least one of a rosin resin and a ketone resin. In the present invention, by incorporating a specific resin selected from a rosin resin or a ketone resin in addition to a chlorinated polyolefin resin into the anchor coat layer-forming composition, it is possible to produce a laminate that has the adhesion of a laminate film, and also has improved printability in areas where ink is reapplied and scratch resistance in areas where ink is not reapplied, as will be shown in the examples below.

[0010] <Binder resin> The binder resin according to the present invention contains a chlorinated polyolefin resin and at least one of a rosin resin and a ketone resin. More preferred embodiments of the binder resin according to the present invention include binder resins containing chlorinated polyolefin resins, rosin-based resins, and ketone resins.

[0011] The binder resin according to the present invention may further contain at least one resin selected from the group consisting of a cellulose resin, a polyurethane resin, a polyamide resin, an acrylic resin, and a polyester resin. Alternatively, the binder resin according to the present invention may contain, in addition to the chlorinated polyolefin resin and the rosin-based resin or the ketone resin, as a further additional component, at least one resin selected from the group consisting of an alkyd resin, a chlorinated rubber, a butyral, and a petroleum resin, in addition to the cellulose-based resin, the polyurethane resin, the polyamide resin, the acrylic resin, the polyester resin, or the cyclized rubber. The binder resin is contained in the anchor coat layer forming composition in an amount of preferably 10.0 to 30.0% by mass, and more preferably 15.0 to 25.0% by mass.

[0012] <<Chlorinated polyolefin resin>> The anchor coat layer-forming composition contains a chlorinated polyolefin resin as a binder resin component. The chlorinated polyolefin resin according to the present invention is not particularly limited as long as it is a polyolefin resin in which at least a portion of the hydrogen atoms have been substituted with chlorine atoms. Examples of chlorinated polyolefin resins include chlorinated polyethylene, chlorinated polypropylene, and acrylic-modified or urethane-modified chlorinated polyolefin resins obtained by modifying chlorinated polyethylene or chlorinated polypropylene with an acrylic polymer or urethane polymer having an ethylenically unsaturated bond. The weight average molecular weight of the chlorinated polyolefin resin is preferably from 5,000 to 300,000, more preferably from 40,000 to 220,000, and even more preferably from 50,000 to 150,000. Furthermore, the chlorine content of the chlorinated polyolefin resin is preferably 15 to 45% by mass to improve adhesion to substrates. From the viewpoint of solubility in organic solvents, the chlorine content is more preferably 26 to 43% by mass. Here, the chlorine content refers to the mass % content of chlorine atoms in 100% by mass of the chlorinated polyolefin resin. The chlorinated polyolefin resin is contained in the anchor coat layer forming composition in an amount of preferably 10.0 to 29.0 mass %, more preferably 10.0 to 25.0 mass %, in terms of solid content. The chlorinated polyolefin resin is preferably contained in an amount of 50.0 to 95.0 mass % relative to 100 mass % of the binder resin in the anchor coat layer-forming composition, and more preferably contained in an amount of 60.0 to 80.0 mass % in terms of solid content.

[0013] <<Rosin-based resin>> The anchor coat layer-forming composition contains at least one of a rosin-based resin and the following ketone resin as a binder resin component. The rosin-based resin used in the present invention can be any commonly used rosin and / or a commonly used rosin derivative, without any particular limitations. Specifically, the rosin or rosin derivative is a rosin or a carboxyl group-containing derivative thereof. Examples of the rosin include gum rosin, wood rosin, tall oil rosin, disproportionated rosin, hydrogenated rosin, and polymers thereof. Examples of the rosin derivative include a carboxyl group-containing derivative such as a rosin derivative to which an unsaturated carboxylic acid such as maleic acid, fumaric acid, itaconic acid, or crotonic acid has been added. In the present invention, the rosin-based resin is preferably a rosin-based acid resin. In the present invention, it is particularly preferable to use a rosin-modified maleic acid resin, which is a maleic acid derivative of rosin, or a rosin-modified fumaric acid resin, which is a fumaric acid derivative of rosin. The rosin-modified maleic acid resin or rosin-modified fumaric acid resin used in the present invention is not particularly limited, and any known rosin-modified maleic acid resin or rosin-modified fumaric acid resin can be used. The rosin-modified maleic acid resin or rosin-modified fumaric acid resin preferably has an acid value of 25 mgKOH / g or more and 320 mgKOH / g or less, and particularly preferably has an acid value of 100 mgKOH / g or more and 320 mgKOH / g or less. As the rosin-based acid resin, for example, the Marquid series manufactured by Arakawa Chemical Industries, Ltd. can be used.

[0014] <<Ketone resin>> The anchor coat layer-forming composition contains at least one of the above-mentioned rosin-based resin and ketone resin as a binder resin component. Examples of the ketone resin of the present invention include condensates of methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone and / or methylcyclohexanone with formaldehyde. As the ketone resin, for example, the TEGO series manufactured by Evonik can be used.

[0015] At least one of the rosin resin and the ketone resin is contained in the anchor coat layer forming composition in an amount of preferably 10.0 to 40.0 mass %, more preferably 15.0 to 35.0 mass %. When both a rosin resin and a ketone resin are contained, the above-mentioned preferable content range is the total content of both resins. When the binder resin in the anchor coat layer-forming composition contains a chlorinated polyolefin resin, a rosin-based resin, and a ketone resin, the content ratio of the chlorinated polyolefin resin, the rosin-based resin, and the ketone resin is preferably 60.0-80.0:15.0-35.0:1.0-10.0 by mass.

[0016] As described above, the binder resin according to the present invention may further contain at least one resin selected from the group consisting of cellulose resin, polyurethane resin, polyamide resin, acrylic resin, polyester resin, and cyclized rubber.

[0017] <<Cellulose-based resin>> Examples of cellulose-based resins include cellulose acetate propionate, cellulose acetate butyrate, and other cellulose ester resins, nitrocellulose (also known as soluble cellulose), hydroxyalkyl cellulose, and carboxyalkyl cellulose. The cellulose ester resin preferably has an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and a hexyl group, and the alkyl group may further have a substituent. Of the above, cellulose acetate propionate, cellulose acetate butyrate, and nitrocellulose are preferred as cellulose-based resins. Nitrocellulose is particularly preferred. The weight-average molecular weight is preferably 5,000 to 200,000, more preferably 10,000 to 50,000. The glass transition temperature is preferably 120°C to 180°C. Nitrocellulose (nitrocellulose) is preferably obtained as a nitric acid ester by reacting natural cellulose with nitric acid to replace three hydroxyl groups in the six-membered ring of the anhydroglucopyranose group in the natural cellulose with nitric acid groups.

[0018] <<Polyurethane resin>> The polyurethane resin is not particularly limited as long as it is a polyurethane resin obtained by reacting a polyol with a polyisocyanate. As the polyol, for example, various known polyols generally used in the production of polyurethane resins can be used, and one or more of them may be used in combination. For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol, Saturated or unsaturated low molecular weight polyols (1) such as ethylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, and pentaerythritol; these low molecular weight polyols (1) and sebacic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, and trimellitic acid polyester polyols (2) obtained by dehydration condensation or polymerization of polycarboxylic acids such as methyl acrylate, pyromellitic acid, or their anhydrides; polyester polyols (3) obtained by ring-opening polymerization of cyclic ester compounds, for example, lactones such as polycaprolactone, polyvalerolactone, and poly(β-methyl-γ-valerolactone); polycarbonate polyols (4) obtained by reacting the above-mentioned low-molecular-weight polyols (1) with, for example, dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, or the like; polybutadiene glycols (5); glycols (6) obtained by adding ethylene oxide or propylene oxide to bisphenol A; and acrylic polyols (7) obtained by copolymerizing, in one molecule, one or more hydroxyethyl groups, hydroxypropyl acrylate, hydroxybutyl acrylate, etc., or the corresponding methacrylic acid derivatives, with, for example, acrylic acid, methacrylic acid, or an ester thereof.

[0019] Examples of polyisocyanates include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of polyurethane resins. For example, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-2,5-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3-dimethyl-2,4-phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1-methyl-3,5-diethylbenzene Aromatic polyisocyanates such as zenediisocyanate, 3-methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5-triethylbenzene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 1-methyl-naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 1,1-dinaphthyl-2,2'-diisocyanate, biphenyl-2,4'-diisocyanate, biphenyl-4,4'-diisocyanate, 3-3'-dimethylbiphenyl-4,4'-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, and diphenylmethane-2,4-diisocyanate;Aliphatic or alicyclic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-di(isocyanatomethyl)cyclohexane, 1,4-di(isocyanatomethyl)cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, and 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate can be used. These polyisocyanates can be used alone or in combination of two or more. Among these, these diisocyanate compounds can be used alone or in combination of two or more. Chain extenders can also be used. Examples of chain extenders include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, and dicyclohexylmethane-4,4'-diamine, as well as amines having a hydroxyl group in the molecule, such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine. These chain extenders can be used alone or in combination of two or more. Monovalent active hydrogen compounds can also be used as end-capping agents for the purpose of terminating the reaction. Examples of such compounds include dialkylamines such as di-n-butylamine and alcohols such as ethanol and isopropyl alcohol. Furthermore, when it is particularly desired to introduce carboxyl groups into the polyurethane resin, amino acids such as glycine and L-alanine can be used as reaction terminators. These end-capping agents can be used alone or in combination. The weight average molecular weight of the polyurethane resin is preferably 10,000 to 100,000, and more preferably in the range of 15,000 to 80,000.

[0020] <<Polyamide resin>> The polyamide resin is, for example, a thermoplastic polyamide soluble in an organic solvent, obtainable by polycondensation of a polybasic acid and a polyamine. In particular, a polyamide resin containing a reaction product of an acid component containing a polymerized fatty acid and / or a dimer acid with an aliphatic and / or aromatic polyamine is preferred, and one containing a portion of primary and secondary monoamines is even more preferred. Polybasic acids used as raw materials for polyamide resins include, but are not limited to, adipic acid, sebacic acid, azelaic acid, phthalic anhydride, isophthalic acid, suberic acid, glutaric acid, fumaric acid, pimelic acid, oxalic acid, malonic acid, succinic acid, maleic acid, terephthalic acid, 1,4-cyclohexyldicarboxylic acid, trimellitic acid, dimer acid, hydrogenated dimer acid, and polymerized fatty acid. Among these, polyamide resins containing a structure derived from dimer acid or polymerized fatty acid as the main component (50% by weight or more in the polyamide resin) are preferred. Here, polymerized fatty acid is obtained by, for example, the cyclization reaction of unsaturated fatty acid, and includes monobasic fatty acid, dimerized polymerized fatty acid (dimer acid), trimerized polymerized fatty acid, and the like. Fatty acids constituting dimer acid or polymerized fatty acid include those derived from natural oils such as soybean oil, palm oil, and rice bran oil, with those derived from oleic acid and linoleic acid being preferred. The polybasic acid may be used in combination with a monocarboxylic acid, such as acetic acid, propionic acid, lauric acid, palmitic acid, benzoic acid, or cyclohexanecarboxylic acid. Examples of polyamines include polyamines and primary or secondary monoamines. Examples of polyamines used in polyamide resins include aliphatic diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, and methylaminopropylamine, and aliphatic polyamines such as diethylenetriamine and triethylenetetramine. Examples of alicyclic polyamines include cyclohexylenediamine and isophoronediamine. Examples of aromatic aliphatic polyamines include xylylenediamine, and examples of aromatic polyamines include phenylenediamine and diaminodiphenylmethane. Examples of primary and secondary monoamines include n-butylamine, octylamine, diethylamine, monoethanolamine, monopropanolamine, diethanolamine, and dipropanolamine.

[0021] <<Acrylic resin>> The acrylic resin is not particularly limited as long as it is a copolymer of polymerizable monomers whose main component is a (meth)acrylic acid ester. Examples of polymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, iso-octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, iso-nonyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and phenoxyethyl (meth)acrylate. The polymerization method is also not particularly limited, and those obtained by known methods such as bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be used. The weight average molecular weight of the acrylic resin is preferably 5,000 to 200,000, and more preferably in the range of 10,000 to 100,000.

[0022] <<Polyester resin>> The polyester resin is not particularly limited as long as it is a polyester resin obtained by reacting an alcohol with a carboxylic acid using a known esterification polymerization reaction. Examples of alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,2-pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaerythritol, 1,4-cyclohexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, spiroglycol, and isosorbide. These may be used alone or in combination of two or more. Among these, polyfunctional alcohols are preferred. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, linoleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, and 1,4-cyclohexanedicarboxylic acid. These may be used alone or in combination of two or more. Among these, polyfunctional carboxylic acids are preferred. The weight average molecular weight of the polyester resin is preferably 500 to 6,000, and more preferably 1,400 to 5,500.

[0023] <<Cyclated rubber>> Cyclized rubber is a polydiene rubber with unsaturated bonds formed by addition polymerization of diene monomers such as butadiene, and then this unsaturated bond is further reacted with an acid catalyst or the like to cyclize some of it.

[0024] <Organic solvents> The organic solvent according to the present invention is not particularly limited, but preferably contains at least one of an aliphatic hydrocarbon solvent, an ester solvent, an alcohol solvent, and a glycol ether solvent. The solvents can be used alone or in combination of two or more. For example, by using an alcohol-based solvent in addition to an ester-based solvent, deterioration of the flexographic plate during flexographic printing can be suppressed. Examples of organic solvents used in the present invention include aliphatic hydrocarbon organic solvents such as hexane, methylcyclohexane, heptane, octane, and decane; ester solvents such as methyl acetate, ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, amyl acetate, ethyl formate, and butyl propionate; alcohol solvents such as methanol, ethanol, propanol, butanol, and isopropyl alcohol; and glycol ether solvents such as ethylene glycol (mono- and di-)methyl ether, ethylene glycol (mono- and di-)ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono- and di-)methyl ether, diethylene glycol (mono- and di-)ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono- and di-)methyl ether, propylene glycol (mono- and di-)methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol (mono- and di-)methyl ether.

[0025] The organic solvent is contained in the anchor coat layer-forming composition in an amount of preferably 40.0 to 90.0 mass %, more preferably 60.0 to 80.0 mass %.

[0026] The anchor coat layer-forming composition of the present invention may further contain at least one of wax and silica.

[0027] <Wax> The anchor coat layer forming composition may contain a wax. As the wax, for example, it is preferable to use polyolefin wax or fatty acid amide wax. Examples of polyolefin waxes include oxidized polyethylene wax and oxidized polypropylene wax. Examples of fatty acid amide waxes include saturated fatty acid amides such as stearic acid amide and palmitic acid amide, unsaturated fatty acid amides such as erucic acid amide, substituted amides, and aromatic amides.

[0028] The anchor coat layer can be formed by applying the anchor coat layer-forming composition of the present invention to a substrate such as a polyolefin film (for example, a heat-shrinkable polyolefin film) and drying the coating film. The thickness of the anchor coat layer is not particularly limited, but is preferably 0.01 μm to 3 μm, and more preferably 0.05 μm to 2 μm, for example.

[0029] (Laminate) The laminate of the present invention has an anchor coat layer formed using the anchor coat layer-forming composition of the present invention. The laminate of the present invention is formed by laminating a polyolefin film, an anchor coat layer, and an ink layer in this order.

[0030] <Layer structure of laminate> As described above, the laminate of the present invention is formed by laminating the polyolefin film / anchor coat layer / ink layer in this order. By using the composition for forming an anchor coat layer of the present invention, adhesion between the anchor coat layer and the polyolefin film substrate is good, ink transferability on the anchor coat layer in areas where ink is reapplied is improved, and scratch resistance of the anchor coat layer in areas where ink is not reapplied is improved. A more preferred embodiment of the laminate of the present invention is, for example, a laminate in which a polyolefin film, an anchor coat layer, a design print layer, and a second print layer, a white print layer, are laminated in this order. For example, the anchor coat layer is provided directly in contact with the back surface of the polyolefin film, the design printing layer is provided directly in contact with the back surface of the anchor coat layer, and the second printing layer (white printing layer) is provided directly in contact with the back surface of the design printing layer.

[0031] <Polyolefin film> As the polyolefin film, a film made of a thermoplastic resin containing an olefin-based resin as a main component can be used. Specific examples of olefin resins include polyethylenes such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene; polypropylene; ethylene-propylene copolymers; α-olefin polymers; ethylene-vinyl acetate copolymers; ethylene-vinyl alcohol copolymers; ethylene-acrylic acid copolymers; ethylene-methyl methacrylate copolymers; ethylene-ethyl acrylate copolymers; cyclic olefin resins; ionomer resins; and polymethylpentene-based olefin resins modified with acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, or other unsaturated carboxylic acids. Preferred polyolefin resins include biaxially oriented polypropylene (OPP), unoriented polypropylene (CPP), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE), as well as acid-modified polyethylene, acid-modified polypropylene, and copolymer polypropylene.

[0032] It is also preferable to use a film formed from a material containing biomass-derived components as the polyolefin film. Biomass films are commercially available from various companies, and for example, sheets such as those listed in the list of biomass-certified products listed by the Japan Organics Recycling Association can be used.

[0033] Specifically, well-known films are made from biomass-derived ethylene glycol. Biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass as a raw material. For example, biomass-derived ethylene glycol can be obtained by converting biomass ethanol into ethylene oxide by a conventionally known method to produce ethylene glycol. Alternatively, commercially available biomass ethylene glycol may be used; for example, biomass ethylene glycol commercially available from India Glycoal Limited can be suitably used.

[0034] Alternatively, products made from biomass materials that are classified by the biomass plastic degree specified in ISO 16620 or ASTM D6866 are also available. In the atmosphere, radioactive carbon is present at a rate of 1 in 1012 particles. 14 Since the ratio of carbon dioxide in the atmosphere is the same as that in plants, the ratio remains the same even in plants that fix carbon dioxide through photosynthesis. For this reason, the carbon in plant-derived resins contains radioactive carbon. 14 In contrast, the carbon in fossil fuel-derived resins contains radioactive carbon. 14 Therefore, radioactive carbon in the resin was measured using an accelerator mass spectrometer. 14The proportion of plant-derived resin in the resin, i.e., the biomass plastic content, can be determined by measuring the concentration of C. Examples of plant-derived low-density polyethylene, which is a biomass plastic having a biomass plastic content of 80% or more, preferably 90% or more as specified by ISO 16620 or ASTM D6866, include Braskem products under the trade names "SBC818," "SPB608," "SBF0323HC," "STN7006," "SEB853," and "SPB681," and films using these as raw materials can be suitably used.

[0035] For example, as an alternative to conventional polyolefin films made from petroleum-based raw materials, biomass polyolefin films such as biomass polyethylene films and biomass polyethylene-polypropylene films containing polyethylene resins made from biomass-derived ethylene glycol are also known. The polyethylene resin is not particularly limited except that ethylene glycol derived from biomass is used as part of the raw material, and examples thereof include ethylene homopolymers and copolymers of ethylene and α-olefins with ethylene as the main component (ethylene-α-olefin copolymers containing 90% by mass or more of ethylene units), and these can be used alone or in combination of two or more. The α-olefin constituting the copolymer of ethylene and α-olefin is not particularly limited, and examples thereof include α-olefins having 4 to 8 carbon atoms such as 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. Known polyethylene resins such as low-density polyethylene resin, medium-density polyethylene resin, and linear low-density polyethylene resin can be used. Among them, linear low-density polyethylene resin (LLDPE) (a copolymer of ethylene and 1-hexene or a copolymer of ethylene and 1-octene) is preferred from the viewpoint of making it even more difficult for damage such as holes or tears to occur even when films rub against each other, and has a density of 0.910 to 0.925 g / cm 3 More preferred is a linear low density polyethylene resin in which

[0036] The biomass film may be a laminate of multiple biomass films, or may be a laminate of a conventional petroleum-based film and a biomass film.

[0037] The polyolefin film substrate can be produced from the above-mentioned resins by a conventionally known film-forming method such as extrusion, cast molding, T-die, cutting, inflation, etc. The film may be an unstretched film, or may be one that has been stretched uniaxially or biaxially using a tenter system, a tubular system, or the like, from the viewpoint of the strength, dimensional stability, and heat resistance of the polyolefin film.

[0038] The polyolefin film may contain additives as needed. Specifically, plastic compounding agents and additives such as elastomers, lubricants, crosslinking agents, antioxidants, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, and pigments may be added for the purpose of improving or modifying processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold releasability, flame retardancy, mildew resistance, electrical properties, strength, etc. The amount of the additive is adjusted within a range that does not affect other performances or recyclability. For example, by incorporating titanium oxide into polyolefin, the film may be colored milky white.

[0039] The thickness of the polyolefin film substrate is not particularly limited and may be appropriately selected from the range of 0.1 to 300 μm from the viewpoints of formability and transparency. It is preferably in the range of 0.3 to 100 μm. If the thickness is less than 0.1 μm, the strength may be insufficient, and if it exceeds 300 μm, the rigidity may be too high, making processing difficult.

[0040] The polyolefin film may be either a heat-shrinkable polyolefin film or a non-heat-shrinkable polyolefin film, and may be appropriately selected taking into consideration the application method and usage form of the polyolefin film.

[0041] <<Heat-shrinkable polyolefin film>> Heat shrinkability refers to the property of shrinking when heated to a required temperature (for example, 70°C to 160°C). A heat-shrinkable polyolefin film heat-shrinks in at least one direction (first direction) within its plane, and preferably heat-shrinks in two orthogonal directions (first direction and second direction) within its plane.

[0042] The heat-shrinkable polyolefin film is a colorless or colored transparent heat-shrinkable film in which the main component resin constituting the film is a polyolefin-based resin. The heat-shrinkable polyolefin film is not particularly limited, and examples thereof include a polypropylene film made of polypropylene and a polyethylene film made of polyethylene, with a polypropylene film being preferred. Examples of polypropylene include propylene homopolymers and propylene-ethylene copolymers, and examples of polyethylene include polyethylene homopolymers and polyethylene copolymers. The thickness of the heat-shrinkable polyolefin film is not particularly limited, and is, for example, preferably 10 μm to 60 μm, more preferably 12 μm to 40 μm.

[0043] <Ink layer> The ink layer according to the present invention may be an ink layer formed using a solvent ink (an ink using an organic solvent, also referred to as an oil-based ink in this specification) or an ink layer formed using a water-based ink. The ink layer according to the present invention may be a single layer or may be formed from two or more layers. For example, the ink layer may be an ink layer consisting of two or more ink layers, including a design printed layer that displays various design displays such as a product name, a pattern, ingredient information, a barcode, a two-dimensional code, and cautionary notes, and a second printed layer that is colorless and transparent, colored and transparent, a single color without a pattern, or multiple colors without a pattern. The design print layer and the second print layer may be made up of a plurality of layers.

[0044] As described above, the design print layer is a print layer on which various design displays such as product names, pictures, ingredient labels, bar codes, two-dimensional codes, and warnings are displayed. The design print layer includes a binder resin and a colorant. As the colorant, a conventionally known pigment or dye can be used.

[0045] As described above, the second printed layer is a colorless and transparent, colored and transparent, a single-colored and patternless printed layer, or a multicolored and patternless printed layer. The second print layer includes a binder resin and an inorganic pigment. Examples of inorganic pigments include colored pigments such as titanium oxide, zinc oxide, aluminum oxide, red iron oxide, antimony red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, and graphite; extender pigments such as silica, calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, and talc; and pearl pigments such as mica and metal oxide-coated mica. These inorganic pigments can be used alone or in combination. Among these, the inorganic pigment preferably contains at least one selected from metal oxides such as titanium oxide, zinc oxide, and aluminum oxide, silica, calcium carbonate, and mica, and more preferably contains titanium oxide.

[0046] The colorant contained in the design print layer is preferably, for example, a pigment, and examples thereof include inorganic pigments and organic pigments used in general inks, paints, recording agents, etc. Examples of organic pigments include soluble azo-based, insoluble azo-based, azo-based, phthalocyanine-based, halogenated phthalocyanine-based, anthraquinone-based, anthanthrone-based, dianthraquinonyl-based, anthrapyrimidine-based, perylene-based, perinone-based, quinacridone-based, thioindigo-based, dioxazine-based, isoindolinone-based, quinophthalone-based, azomethine azo-based, flavanthrone-based, diketopyrrolopyrrole-based, isoindoline-based, indanthrone-based, and carbon black-based pigments. Other examples include carmine 6B, lake red C, permanent red 2B, disazo yellow, pyrazolone orange, carmine FB, cromophtal yellow, cromophtal red, phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone magenta, quinacridone red, indanthrone blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, daylight fluorescent pigments, etc. In addition, both non-acid-treated pigments and acid-treated pigments can be used.

[0047] Whether it is the design printing layer or the second printing layer, the ink (also called the ink composition) that forms the printing layer is composed of a colorant such as the pigment mentioned above, a binder resin, a solvent, and various other additives as necessary. When the ink is a solvent ink, examples of the binder resin contained in the solvent ink include at least one of ketone resin, cellulose resin, and polyamide resin, or a urethane resin or acrylic resin binder resin, etc. Here, the ketone resin, cellulose resin, polyamide resin, urethane resin, and acrylic resin are as described in the explanation of each resin in the above-mentioned <Binder Resin> section. When the ink is a solvent ink, examples of the solvent contained in the solvent ink include the organic solvents described above.

[0048] When the ink is an aqueous ink, the binder resin contained in the aqueous ink may be a water-dispersible or water-soluble resin, such as an acrylic resin or a urethane resin that is used in general aqueous liquid printing inks. The acrylic resin is not particularly limited, and examples thereof include a homopolymer or copolymer of (meth)acrylate, and a copolymer of a vinyl monomer copolymerizable with (meth)acrylate. Furthermore, a copolymer having an acid value is preferred for the purpose of imparting water dispersibility or water solubility. The urethane resin is not particularly limited, and examples thereof include urethane resins obtained by reacting a polyol such as polyether polyol, polyester polyol, or polycarbonate polyol with a polyol having a hydrophilic group such as an anionic group, a cationic group, a polyoxyethylene group, or a polyoxyethylene-polyoxypropylene group, and a polyisocyanate. The weight-average molecular weight of the urethane resin is not particularly limited, but generally, it should be 5,000 to 200,000, and preferably 20,000 to 150,000. When the ink is an aqueous ink, examples of the solvent (aqueous medium) contained in the aqueous ink include water, organic solvents that are miscible with water, and mixtures thereof. Examples of organic solvents that are miscible with water include alcohol solvents such as methanol, ethanol, n-propanol, and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol, and propylene glycol; alkyl ethers of polyalkylene glycols; and lactam solvents such as N-methyl-2-pyrrolidone. In the present invention, water alone may be used, or a mixture of water and a water-miscible organic solvent may be used, or a water-miscible organic solvent alone may be used. Furthermore, as the aqueous medium, from the viewpoints of safety and environmental load, water alone or a mixture of water and a water-miscible organic solvent is preferred, and water alone is more preferred.

[0049] As described above, the ink composition may contain various additives, and may further contain, for example, at least one of wax and silica. The wax contained in the ink composition is as described above in the section <Wax> of (Anchor coat layer forming composition).

[0050] The design print layer can be formed by printing an ink containing a binder resin and a colorant using a known printing method. The second printed layer can be formed by printing an ink containing a binder resin and an inorganic pigment using a known printing method. For example, known printing methods include printing with liquid printing inks such as gravure inks and flexographic inks. The thickness of the design print layer is not particularly limited, but is preferably, for example, 0.1 μm to 5 μm, and the thickness of the second print layer is not particularly limited, but is preferably, for example, 0.5 μm to 5 μm.

[0051] <<Preferred embodiment of the ink layer>> Preferred embodiments of the laminate including the ink layer include, for example, the following embodiments (i) and (ii). (i) Polyolefin film / solvent (oil-based) anchor coat layer / solvent (oil-based) ink layer (ii) Polyolefin film / solvent (oil-based) anchor coat layer / water-based ink layer Considering the demand for the use of aqueous solvents from an environmental perspective, the above embodiment (ii) is preferred. A method for producing an aqueous ink involves, for example, dispersing a pigment, water alone or a mixture containing a water-miscible organic solvent, a pigment dispersant, an antifoaming agent, etc., in a disperser to obtain a pigment dispersion. To the resulting pigment dispersion, a binder resin, water or a water-miscible organic solvent, and optionally additives such as a leveling agent, are added, followed by stirring and mixing to obtain an ink composition. Examples of dispersers commonly used in the production of gravure and flexographic printing inks include a bead mill, Eiger mill, sand mill, gamma mill, and attritor.

[0052] <Method of manufacturing laminate> The laminate of the present invention can be produced, for example, as follows. The anchor coat layer-forming composition is applied to a polyolefin film substrate, and the coating film is dried to form an anchor coat layer. An ink (ink composition) is applied onto the anchor coat layer, and the coating film is dried to form an ink layer. Furthermore, by changing the type of ink, multiple ink layers (printed layers) can be formed in sequence, from the first ink layer (first printed layer) to the second ink layer (second printed layer), and then, as appropriate, the third ink layer (third printed layer), the fourth ink layer (fourth printed layer), etc.

[0053] <Application of laminates> The laminate of the present invention is used, for example, as an overwrap film for overwrap packaging, particularly for packaging cup noodles. The overlap film according to the present invention is used by being attached to various adherends by heat shrinking. An overlap film is used as a protective film by wrapping it around a single adherend, or as a protective and bundling film by wrapping it around an assembly of multiple adherends. The adherend is not particularly limited, and may be a container in which an article is stored, or the article itself. Examples of the substrate include containers containing instant foods such as instant noodles, dairy products such as yogurt, luxury foods such as jellies and puddings, beverages, seasonings, sanitary products such as shampoo, and fresh foods such as meat; and articles themselves such as dry batteries. When the adherend is a container containing an article, the external shape of the container is not particularly limited, and examples thereof include cylindrical shapes such as a cylindrical, elliptical, or rectangular cylinder; inverted truncated cone shapes such as an inverted truncated elliptical cone shape or an inverted truncated square pyramid; and irregular shapes such as a gourd shape. The material of the container is not particularly limited, and examples thereof include synthetic resin, foamed synthetic resin, metal, glass, ceramic, and wood.

[0054] <<Specific uses of overlap film>> In mechanical manufacturing processes, packages in which an adherend is wrapped in overlap film are usually produced as follows: For example, a long overlap film is formed into a cylindrical shape so as to wrap around the adherend, and both side edges along the MD (longitudinal direction) are heat-sealed, and the long overlap film formed into a cylindrical shape wrapping the adherend is thermally sealed in the TD on both the front and rear sides of the adherend, and then the overlap film, sealed on three sides with the adherend inside, is heated to heat shrink the package, thereby obtaining a package. [Example]

[0055] The present invention will be described in more detail below using examples. Of course, the present invention should not be limited to the scope of these examples. Hereinafter, "parts" and "%" are by mass unless otherwise specified.

[0056] (Preparation of various compositions) As compositions for forming an anchor coat layer, oil-based anchor coat varnishes of Preparation Examples AC1 to AC4 shown in Table 1 below were prepared. As the inks, oil-based color inks of Preparation Example Color 1 to Preparation Example Color 3 shown in Table 2 below were prepared. As the inks, oil-based white inks of Preparation Example-White 1 to Preparation Example-White 3 shown in Table 3 below were prepared. As the inks, the water-based color inks of Preparation Example Color 4 to Preparation Example Color 5 shown in Table 4 below were prepared. As the inks, water-based white inks of Preparation Example White 4 to Preparation Example White 5 shown in Table 5 below were prepared.

[0057] [Table 1]

[0058] The raw materials used in the table are as follows: Chlorinated polypropylene resin: Nippon Paper Industries Co., Ltd. "Super Chlon 360T, 60% solids" Rosin-modified maleic acid resin: "Marquid No. 31" manufactured by Arakawa Chemical Industries, Ltd. Ketone formaldehyde resin: Commercially available 100% solid ketone formaldehyde resin Cyclized rubber: Commercially available cyclized rubber with 100% solids content Silica: Fuji Silysia Chemical "Sylysia 436"

[0059] <Preparation Example - AC1> 23.6 parts of chlorinated polyolefin resin solution (solid content 60%), 4.7 parts of rosin-modified maleic acid resin solid content, 0.9 parts of ketone formaldehyde resin solid content, 1.1 parts of cyclized rubber solid content, 37.7 parts of methylcyclohexane, 19.0 parts of normal propyl acetate, 11.5 parts of normal propyl alcohol, and 1.5 parts of silica were stirred to prepare Preparation Example-AC1.

[0060] <Preparation example-AC2> 25.0 parts of chlorinated polyolefin resin solution (solid content 60%), 4.7 parts of rosin formaldehyde resin solid content, 1.1 parts of cyclized rubber solid content, 37.7 parts of methylcyclohexane, 18.4 parts of normal propyl acetate, 11.5 parts of normal propyl alcohol, and 1.5 parts of silica were stirred to prepare Preparation Example-AC2.

[0061] <Adjustment example-AC3> 25.0 parts of chlorinated polyolefin resin solution (solid content 60%), 4.7 parts of ketone-modified maleic acid resin solid content, 1.1 parts of cyclized rubber solid content, 37.7 parts of methylcyclohexane, 18.4 parts of normal propyl acetate, 11.5 parts of normal propyl alcohol, and 1.5 parts of silica were stirred to prepare Preparation Example-AC3.

[0062] <Adjustment example-AC4> 32.9 parts of chlorinated polyolefin resin solution (solid content 60%), 1.1 parts of cyclized rubber solid content, 37.7 parts of methylcyclohexane, 15.2 parts of normal propyl acetate, 11.5 parts of normal propyl alcohol, and 1.5 parts of silica were stirred to prepare Preparation Example-AC4.

[0063] [Table 2]

[0064] In the table, the following raw materials were used: Carbon black: Orion Engineered Carbons "Special Black 250 Powder" Nitrocellulose resin: NOBEL "NITROCELLULOSE DHX3-5" Polyamide resin: Commercially available 100% solid polyamide resin Ketone formaldehyde resin: Commercially available 100% solid ketone formaldehyde resin Urethane resin: DIC "Burnoch ECL-341" Acrylic resin: Taisei Fine Chemical Co., Ltd. "Acrit Series" Silica: Fuji Silysia Chemical "Sylysia 436"

[0065] <Preparation Example - Color 1> 15.0 parts of carbon black, 8.1 parts of nitrocellulose resin solids, 6.1 parts of polyamide resin solids, 2.4 parts of ketone formaldehyde resin solids, 41.3 parts of normal propyl alcohol, and 26.1 parts of normal propyl acetate were mixed and kneaded, and 1.0 part of silica was added to prepare Preparation Example - Color 1.

[0066] <Preparation Example - Color 2> 15.0 parts of carbon black, 16.5 parts of urethane resin solids, 41.3 parts of normal propyl alcohol, and 26.1 parts of normal propyl acetate were mixed and kneaded, and 1.0 part of silica was added to prepare Preparation Example Color 2.

[0067] <Preparation Example - Color 3> 15.0 parts of carbon black, 16.5 parts of acrylic resin solids, 41.3 parts of normal propyl alcohol, and 26.1 parts of normal propyl acetate were mixed and kneaded, and 1.0 part of silica was added to prepare Preparation Example Color 3.

[0068] [Table 3]

[0069] In the table, the following raw materials were used: Titanium oxide: Teika "TITANIX JR-808" Polyamide resin: Commercially available 100% solid polyamide resin Ketone formaldehyde resin: Commercially available 100% solid ketone formaldehyde resin Nitrocellulose resin: NOBEL "NITROCELLULOSE DHX3-5" Urethane resin: DIC "Burnoch ECL-341" Acrylic resin: Taisei Fine Chemical Co., Ltd. "Acrit Series" Silica: Fuji Silysia Chemical "Sylysia 436" Paraffin wax: Accumelt 8756A manufactured by THE INTERNATIONAL GR

[0070] <Preparation example-white 1> 51.8 parts of titanium oxide, 6.8 parts of polyamide resin solids, 3.3 parts of ketone formaldehyde resin solids, 2.0 parts of nitrocellulose resin solids, 21.2 parts of normal propyl alcohol, 5.8 parts of methylcyclohexane, and 5.0 parts of normal propyl acetate were mixed and kneaded, and 2.5 parts of silica and 1.5 parts of paraffin wax were added to produce Preparation Example - White 1.

[0071] <Preparation example-white 2> 51.8 parts of titanium oxide, 12.1 parts of urethane resin solids, 21.2 parts of normal propyl alcohol, 5.8 parts of methylcyclohexane, and 5.0 parts of normal propyl acetate were mixed and kneaded, and 2.5 parts of silica and 1.5 parts of paraffin wax were added to produce Preparation Example - White 2.

[0072] <Preparation example-white 3> 51.8 parts of titanium oxide, 12.1 parts of acrylic resin solids, 21.2 parts of normal propyl alcohol, 5.8 parts of methylcyclohexane, and 5.0 parts of normal propyl acetate were mixed and kneaded, and 2.5 parts of silica and 1.5 parts of paraffin wax were added to prepare Preparation Example 3.

[0073] [Table 4]

[0074] In the table, the following raw materials were used: Carbon black: CABOT "REGAL 330R Carbon Black" Water-based urethane resin solution: Taisei Fine Chemical Co., Ltd. "Acrit WBR-016U" Water-based acrylic resin solution: BASF "JONCRYL PDX-7741" Polyethylene wax: Mitsui Chemicals "Chemipearl W-400"

[0075] <Preparation Example - Color 4> 20.0 parts of carbon black, 48.8 parts of a commercially available aqueous urethane resin solution with a solid content of 30% containing water, 6.3 parts of normal propyl alcohol, and 23.0 parts of water were mixed and kneaded, and 1.9 parts of polyethylene wax was added to produce Preparation Example - Color 4.

[0076] <Preparation Example - Color 5> 20.0 parts of carbon black, 48.8 parts of a commercially available aqueous acrylic resin solution with a solid content of 30% containing water, 6.3 parts of normal propyl alcohol, and 23.0 parts of water were mixed and kneaded, and 1.9 parts of polyethylene wax was added to produce Preparation Example - Color 5.

[0077] [Table 5]

[0078] In the table, the following raw materials were used: Titanium oxide: Teika "TITANIX JR-808" Water-based urethane resin solution: Taisei Fine Chemical Co., Ltd. "Acrit WBR-016U" Water-based acrylic resin solution: BASF "JONCRYL PDX-7741" Polyethylene wax: Mitsui Chemicals "Chemipearl W-400"

[0079] <Preparation example-white 4> 28.0 parts of titanium oxide, 57.6 parts of a commercially available aqueous urethane resin solution with a solid content of 30% containing water, 4.2 parts of normal propyl alcohol, and 7.2 parts of water were mixed and kneaded, and 3.0 parts of polyethylene wax was added to produce Preparation Example - White 4.

[0080] <Preparation example-white 5> 28.0 parts of titanium oxide, 57.6 parts of a commercially available aqueous acrylic resin solution with a solid content of 30% containing water, 4.2 parts of normal propyl alcohol, and 7.2 parts of water were mixed and kneaded, and 3.0 parts of polyethylene wax was added to produce Preparation Example - White 5.

[0081] (Printing method) The oil-based anchor coat varnish described in Preparation Example was prepared with methylcyclohexane in a Zahn Cup #4 (manufactured by Rigo Co., Ltd.) for 10 seconds (25°C). The inks described in the Preparation Examples (oil-based color ink, oil-based white ink, water-based color ink, water-based white ink) were each prepared using a 50 / 50 mixed organic solvent of normal propyl acetate / n-propyl alcohol in a Zahn Cup #4 (manufactured by Rigo Co., Ltd.) for 10 seconds (25°C). Using a Windmill CI-type 6-color flexographic printing machine SOLOFLEX, various oil-based anchor coat varnishes or inks were printed onto a biaxially oriented polypropylene film (thickness 15 μm) substrate to obtain laminates (printing ink laminates) with the configurations shown in Tables 6 to 8 below. The printing order of the oil-based anchor coat varnish and ink was as shown in Tables 6 to 8, with the anchor coat layer (first printed layer), color ink layer (second printed layer), and white ink layer (third printed layer) printed in that order.

[0082] In Tables 6 to 8, the polyolefin film substrate used in Examples 1 to 10 and Comparative Examples 1 and 2 was a heat-shrinkable polyolefin substrate, and a biaxially oriented polypropylene film (thickness 13.5 μm) manufactured by Kojin Film & Chemicals Co., Ltd. was used. The substrate used in Example 11 was a non-shrink polyolefin CPP substrate, and an unstretched polypropylene film (thickness: 30 μm) manufactured by Futamura Chemical Co., Ltd. was used. The substrate used in Example 12 (an additional example) was a non-shrink polyolefin LLDPE substrate, and a linear low-density polyethylene film (thickness 60 μm) manufactured by RM Tocello Corporation was used.

[0083] The laminates (printing ink laminates) prepared in Tables 6 to 8 were subjected to the following evaluations. However, in Examples 8 to 10 and Comparative Example 2 listed in Tables 8 and 9, in order to evaluate the scratch resistance of areas where ink was not reapplied, an ink layer was not formed, and evaluation was performed on a laminate consisting only of a biaxially oriented polypropylene film substrate and an anchor coat layer (first printing layer).

[0084] (Evaluation of laminate) [Printability (ink transfer)] When the inks were printed using the method described in the above (Printing Method) section, the transferability of various color and white inks onto the anchor coat layer was evaluated visually. -Evaluation criteria- 4. No ink transfer problems observed 3. Poor ink transfer is hardly observed. 2. Slight ink transfer failure is observed. 1 Poor ink transfer is evident

[0085] [Adhesion before shrinkage] After printing the anchor coat layer or ink layer, cellophane tape (manufactured by Nichiban Co., Ltd.) was applied to the printed surface, and the tape was quickly peeled off, and the condition of the printed surface was evaluated visually. The adhesion before shrinkage is evaluated as the adhesion of a laminate (printed material) that is not heated and does not undergo thermal shrinkage after printing. -Evaluation criteria- 3 The printed film does not peel off from the film at all 2 Less than 30% of the printed film surface area peels off from the film. 1 At least 70% of the printed surface area is peeled off from the film.

[0086] [Scratch resistance before shrinkage] The ink layer surface or the anchor coat layer surface of the resulting laminate (printed material) was rubbed with a fingernail 20 times, and the state of removal of the film from the printed surface was visually evaluated. -Evaluation criteria- 3 The printed film does not peel off from the film substrate at all. 2 Less than 30% of the printed film surface area peels off from the film substrate. 1 70% or more of the printed surface area is peeled off from the film substrate.

[0087] [Crush resistance before shrinkage] The ink layer surface or the anchor coat layer surface of the resulting laminate (printed material) was rubbed five times back and forth, and the state of removal of the film from the printed surface was evaluated visually. -Evaluation criteria- 3 The printed film does not peel off from the film substrate at all. 2 Less than 30% of the printed film surface area peels off from the film substrate. 1 70% or more of the printed surface area is peeled off from the film substrate.

[0088] [Adhesion after shrinkage] The resulting laminate (printed material) was shrunk in a thermostatic chamber at 120° C. for 30 seconds. Next, cellophane tape (manufactured by Nichiban Co., Ltd.) was applied to the printed surface, and the tape was quickly peeled off, and the condition of the printed surface was visually evaluated. The post-shrinkage adhesion is an evaluation of the adhesion of a laminate (printed material) that has been heated and thermally shrunk after printing. Therefore, this evaluation was performed only on examples using a heat-shrinkable polyolefin film as the substrate, and was not performed on non-shrinkable polyolefin films, as shrinkage due to heat heating is not anticipated. -Evaluation criteria- 3 The printed film does not peel off from the film substrate at all. 2 Less than 30% of the printed film surface area peels off from the film substrate. 1 70% or more of the printed film surface area peels off from the film substrate.

[0089] [Blocking resistance] The ink layer surface or anchor coat layer surface of the prepared laminate (printed matter) was mated with a film substrate, and left for one day under conditions of pressure: 0.5 MPa, temperature: 40°C, and humidity: 80% using a blocking tester. After the test, the peeling property and condition of the surface were evaluated. -Evaluation criteria- 4 When peeling the printed surfaces apart, there is no resistance and there are no particular problems with the surface. 3 When peeling the printed surfaces apart, there is some resistance and the surfaces are slightly stuck together. 2 When peeling the printed surfaces, there is resistance, but the ink layer or anchor coat layer does not peel off. 1 When peeling the printed surfaces, there is considerable resistance, and the ink layer or anchor coat layer is peeling off.

[0090] [Heat resistance] The ink layer surface or anchor coat layer surface of the prepared laminate (printed material) is aligned with a polystyrene sheet that represents the container in which the printed surface will be accumulated, and pressed together with a heat seal bar at a pressure of 0.1 MPa for 1 second, and the degree to which the film on the printed surface has been removed is confirmed. Test temperature: 120℃ -Evaluation criteria- 4. The printed film does not come off at all on the polystyrene sheet. 3. The printed film is less than 30% of the surface area of ​​the polystyrene sheet. 2. The printed film covers less than 50% of the surface area of ​​the polystyrene sheet. 1. The printed film covers 70% or more of the surface area of ​​the polystyrene sheet.

[0091] (Examples 1 to 12, Comparative Examples 1 and 2) The evaluation results for the laminates (printed materials) of the examples and comparative examples shown in Tables 6 to 8 below are shown in the same tables.

[0092] [Table 6]

[0093] [Table 7]

[0094] [Table 8]

[0095] From the results of Examples 1 to 7, Examples 11 and 12, and Comparative Example 1, it was found that a laminate (printed matter) having an anchor coat layer formed using the anchor coat layer-forming composition of the present invention is a laminate that ensures adhesion as a laminate film while exhibiting good printability (ink transferability) in the areas where ink is reapplied. In Tables 6 to 8, a laminate with a rating of 2 or higher can be considered practically usable. In this regard, Comparative Example 1, which was formed using a composition for forming an anchor coat layer that does not satisfy the requirements of the present invention, did not satisfy the evaluation standard for practical use in terms of printability (ink transferability) in the areas where ink is reapplied (the printability rating of Comparative Example 1 was 1). Furthermore, the results of Examples 8 to 10 and Comparative Example 2 revealed that a laminate (printed material) having an anchor coat layer formed using the anchor coat layer-forming composition of the present invention ensures adhesion as a laminate film while providing good scratch resistance in areas where ink is not recoated. In Tables 6 to 8, a laminate with a rating of 2 or higher can be considered practically usable. In this regard, Comparative Example 2, which was formed using a composition for forming an anchor coat layer that does not satisfy the requirements of the present invention, failed to satisfy the evaluation criteria for practical use in terms of scratch resistance in areas where ink is not recoated (the scratch resistance rating of Comparative Example 2 was 1).

Claims

1. A composition for forming an anchor coat layer for forming an anchor coat layer disposed between a polyolefin film and an ink layer, Contains a binder resin and an organic solvent, The composition for forming an anchor coat layer contains a binder resin selected from the group consisting of a chlorinated polyolefin resin, a rosin resin, and a ketone resin.

2. The anchor coat layer forming composition according to claim 1 , wherein the binder resin further contains at least one resin selected from the group consisting of a cellulose-based resin, a polyurethane resin, a polyamide resin, an acrylic resin, a polyester resin, and a cyclized rubber.

3. The composition for forming an anchor coat layer according to claim 1 , wherein the organic solvent contains at least one of an aliphatic hydrocarbon solvent, an ester solvent, an alcohol solvent, and a glycol ether solvent.

4. The composition for forming an anchor coat layer according to claim 1 , further comprising at least one of wax and silica.

5. A laminate comprising a polyolefin film, an anchor coat layer, and an ink layer laminated in this order, A laminate, wherein the anchor coat layer is a layer formed using the composition for forming an anchor coat layer according to any one of claims 1 to 4.

6. The laminate according to claim 5 , wherein the polyolefin film is a heat-shrinkable film.

7. The laminate according to claim 5 , wherein the ink layer contains at least one of a ketone resin, a cellulose-based resin, and a polyamide resin.

Images